Stereoselective benzylic amination reaction is important for their further application as pharmaceuticals and agrochemicals, and other chemical entities. Herein, we describe the diastereoselective amination of 1,2-anti-dialkoxychromane on chromane framework using chlorosulfonyl isocyanate. Notably, the utility of this protocol is highlighted by the total synthesis of chromanol 293B and cromakalim.